Textile decorating compositions



Ityasalsoproposedatanearlydatetouse .581, ilfllledNoilember 19, 1940;they Patented 12, 1944 UNITED STATE 'rnxmn m-zcona'rmo comosrrrons CarlM. Marberg, Elmhurst, and Earl K. Fischer,

Long Island City, N. Y., assignors to Interchemical Corporation, NewYork, N. Y., a corporation of Ohio I -No Drawing. Application October18,1941,

Serial No. 415,020 2 Claims. (Cl. set-s) This invention is in the fieldof textile printms. in particular of pigment printing. It provides a newtype of pigment printing paste containing as the pigment binder modifiedpolyvinyl high color cost for lightand tub-fast dyes, has

been a major problem in textile printing. An unsolved problem has beenthe reproduction of very fine designs. Since the pastes spread on thefabrig after printing when thin enough to be removed sharply from fineengravings, givin blurred designs, it has been foundimpossible to usephotogravure cylinders or extremely fine mill and die engravings.Attempts to modify these pastes by addition of wetting agents andemulsiflcation of oils therein have not solved the basic difiiculties.

In order to overcome the diiilculty with the '1 use ofdyestufis', it haslong been proposed to use insoluble pigments in printing pastes. Albumenand other water-dispersible thickeners have been used to bind thepigment to'the fabric, the albu-' men being set by heat so as to becomeinsoluble inwater. The resultant prints, however, will not withstandlaundering satisfactorily, and the same printing difficulties areencountered as with dyeordinary oil base printing inks and coloredlacquers in the decoration of fabrics; these compositions were neversatisfactor as a general replacement for dyestuif printing pastes, for avariety of reasons. Relatively few binders useful in printing inks. andlacquers withstand both dry cleaning and washing; and such compositionsas are. resistant have been generally unacceptable due to the fact thatthe fabrics, when printed with lacquers, develop an undesirable stififeel {known to the trade as "hand' to the necessity for using largeamounts of color to obtain deep shades, and to the tendency ofcoloredcible lacquer phase is thickened by an inner aqueous phase which is atleast 20 per cent. of the total emulsion, by weight. Preferably, thebinder of the lacquer is one which is originally soluble in ordinaryorganic solvents and which can be converted into an insoluble stateafter printingmost desirably, a readily heat-polymerizable syntheticresin, best exemplified by the plasticized urea formaldehyde resins.These pastes have not only overcome the problem of hand and crocking,"as relates to pigment printing, but have introduced new printingstandards into the industry, because of their marked superiority inprinting properties as compared to the conventional aqueous systems.

The industry has, however, one objection to 1 these new pastes; theiruse of a continuous hydrophobe phase introduces new problems into anindustry that is accustomed to handling watermiscible materials. .7Hence, theauccess'ful intro- Hduction of these pastes has served tointensify the search for the long sought for wash-fast .albumen, and toraise the standards of washness, are certain cellulose ethers andhydroxy ethers, water-soluble urea formaldehyde resins which are set byheat on the fabric, and polyvinyl alcohols, which are printed incombination with formaldehyde or dimethylol urea, and insolubiiized byreaction between the ingredients induced by heat. None of theseproductahowever, has been used with complete success in pig-- mentprinting, for two reasons-their printing properties. are poor,particularly in that they do not utilize the full color value of thepigments used with them. and their wash fastness, while considerablybetter than albumen, leaves much to be desired.

Attempts to improve the. color value obtained I with polyvinyl alcoholby the addition of waterdispersible thickeners ordinarily produce twoeffects. In the first place, the amount of binder is so markedlyincreased that the prints become 1 'stifi and Secondly, the prints; tendto markings to rub oil on to other clothing andleave a mark (known as"cl-coking) i There has recently appeared on the market a new type orpigmented textile printing paste which has been successful as areplacement for the old type dyestui! printing paste, These pastes aredescribed in the Jenett U. 8. Patent No. 2,222,- are emulsions in whichan outer continuous water-immisbecome more water-sensitive and lessresistant to washing as the binder content increases, ap-

parentlybecause of'reduced adhesion to the fabno in the case ofwater-resistant additions, and

of water-susceptibility with materials such asstarch and thewater-soluble'gums.

We have discovered that substantially improved color value be obtainedin printing with pigmented aqueous polyv nyl alcohol compositions, byincluding in the composition from about 4% to 1% or an alginate,preferably in admixture with a letting agent for the polyv yl alcohol,such as formaldehyde or a water-soluble carbamide resin. f

rhe alginates have the property. in combination with the polyvinylalcohols, of giving increased color value without causing boardiness ofthe prints, and without decreasing the wash-re The melamine-formaldehyderesin is dissolved in cc. oi-the water. The potassium alginate isswelled in the rest of the water, which is sumciently warmed, and thenall the constituents are mixed, under a high-speed stirrer. A paste of Igood printing properties is obtained.

Example 2 i Grams Polyvinyl alcohol (PVA 403), 10% aqueo solution 100Ciba water-soluble melamlne-formalde ,hyde resin I I Tributyl phosphate1 Keltex l Heliogen Blue (22% pulp) 9 Water 85 This gives a blue printwith fairly good color value. Alter heating the prints for five minutesat 250 F., the prints are reasonably wash-resistant.

The tributyl phosphate is used to reduce foamhis.

s eaves i The constituents are mixed under a b-sp stirrer.

Example 4 4 I Grams lolyvinyl'alcohol (PVA 403), 10% aqueous solution100 Keltex (potassium alginate) -i. 2-ethyl hexaldehyde Heliosen GreenG, aqueous-pulp Solvesso #2 (hydrogenated naphtha-B. R.

135-177" C.) 10 Water 75.5

The algina'te is dissolved in the heated water, and the aqueousconstituents are mixed. Then the non-aqueous constituents, previouslymixed, are added slowly with The rmultant emulsion ink is printed oncotton cloth, and gives an excellent print. on heating, the aldehyde re-Tributyl phosphate 1 Keltex (potassium alginate) i Monastral Green, 20%aqueous slurry-- 20 Water 73.5 Pyridine 0.5

acts with the polyvinyl alcohol to produce a product of satisfactorywash iastness.

Changes can of course be made in the examples without departing irom'thescope of the in-- vention. As indicated above, the alginate may m variedas desired; we have used sodium alglnate. a ar and otherisimilarproducts. Polyvinyl alcohols of various molecular weights may be used.

The improvement in color value is observable with or without aninsolubilizing agent. While the products produced are particularlydesirable for printing, they may also be for pigment dyeing, by forcingthe-thickened composition through the fabric, in the manner described'in the Cassel U. 8. Patent No. 2,248,698, issued July 8, 1941. I I

We claim:

1. A textile decorating composition yielding; improved pigment colorvalue on fabric, comprising a pigment dispersed in an aqueous p0 alcoholsolution of such concentration that the composition has cient body to beprintable from an intaglio plate, but which alone yields poor colorvalue on fabric, and from .l% to 1% oi a water-soluble alginate, wherebythe color value obtained issubstantially improved.

2. A textile decorating composition yiel i improved pigment color valueon fabric, comp Example 3 I ing a pigment dispersed in an aqueous 1 1 IG alcohol solution of such concentration that the Polyvinyl alcohol (PVA403), 10% aqueous composition has, sufflcient body to be printablesolution I 0- from an intsglio plate, but which alone yields Agar-agar,dissolved in 2 poor color value on fabric, an insolubilizing at ,Hotwater I for the polyvinyl alcohol, and irom .1% to 1% or a 88%rormaldehyde 15 water-soluble ate, whereby the color value Indian Red.20% pulp 5 o tained is substantially improved. Tributyl phosphate 1Beetle cream (50% aqueous, water-soluble,

urea-formaldehyde partial p0 12 Water 10

